Thermodynamic modelling of an Al(2)O(3)-MnO system using the ionic model

The thermodynamic assessment of an Al(2)O(3)-MnO pseudo-binary system has been carried out with the use of an ionic model. The use of the electro-neutrality principles in addition to the constitutive relations, between site fractions of the species on each sub-lattice, the thermodynamics descriptions of each solid phase has been determined to make possible the solubility description. Based on the thermodynamics descriptions of each phase in addition to thermo-chemical data obtained from the literature, the Gibbs energy functions were optimized for each phase of the Al(2)O(3)-MnO system with the support of PARROT(R) module from ThemoCalc(R) package. A thermodynamic database was obtained, in agreement with the thermo-chemical data extracted from the literature, to describe the Al(2)O(3)-MnO system including the solubility description of solid phases. (C) 2009 Elsevier Ltd. All rights reserved.

Spatial patterns of soil attributes and components in a mangrove system in Southeast Brazil (Sao Paulo)

Purpose Among environmental factors governing innumerous processes that are active in estuarine environments, those of edaphic character have received special attention in recent studies. With the objectives of determining the spatial patterns of soil attributes and components across different mangrove forest landscapes and obtaining additional information on the cause-effect relationships between these variables and position within the estuary, we analyzed several soil attributes in 31 mangrove soil profiles from the state of So Paulo (Guaruja, Brazil). Materials and methods Soil samples were collected at low tide along two transects within the CrumahA(0) mangrove forest. Samples were analyzed to determine pH, Eh, salinity, and the percentages of sand, silt, clay, total organic carbon (TOC), and total S. Mineralogy of the clay fraction (< 2 mm) was also studied by X-ray diffraction analysis, and partitioning of solid-phase Fe was performed by sequential extraction. Results and discussion The results obtained indicate important differences in soil composition at different depths and landscape positions, causing variations in physicochemical parameters, clay mineralogy, TOC contents, and iron geochemistry. The results also indicate that physicochemical conditions may vary in terms of different local microtopographies. Soil salinity was determined by relative position in relation to flood tide and transition areas with highlands. The proportions of TOC and total S are conditioned by the sedimentation of organic matter derived from vegetation and by the prevailing redox conditions, which clearly favored intense sulfate reduction in the soils (similar to 80% of the total Fe is Fe-pyrite). Particle-size distribution is conditioned by erosive/deposition processes (present and past) and probably by the positioning of ancient and reworked sandy ridges. The existing physicochemical conditions appear to contribute to the synthesis (smectite) and transformation (kaolinite) of clay minerals. Conclusions The results demonstrate that the position of soils in the estuary greatly affects soil attributes. Differences occur even at small scales (meters), indicating that both edaphic (soil classification, soil mineralogy, and soil genesis) and environmental (contamination and carbon stock) studies should take such variability into account.

Cu and Fe metallic ions-mediated oxidation of low-density lipoproteins studied by NMR, TEM and Z-scan technique

In this work we report on a study of the morphological changes of LDL induced in vitro by metallic ions (Cu(2+) and Fe(3+)). These modifications were characterized by transmission electron microscopy, nuclear magnetic resonance and the Z-scan technique. The degree of oxidative modification of LDL was determined by the TBARS and lipid hydroperoxides assays. It is shown that distinct pathways for modifying lipoproteins lead to different morphological transformations of the particles characterized by changes in size and/or shape of the resulting particles, and by the tendency to induce aggregation of the particles. There were no evidence of melting of particles promoted by oxidative processes with Cu and Fe. (C) 2010 Elsevier Ireland Ltd. All rights reserved.

(1)H NMR determination of beta-N-methylamino-L-alanine (L-BMAA) in environmental and biological samples

A nuclear magnetic resonance ((1)H NMR) method for the determination of beta-N-methylamino-L-alanine (L-BMAA) in environmental aqueous samples was developed and validated. L-BMAA is a neurotoxic modified amino acid that can be produced by cyanobacteria in aqueous environments. This toxin was extracted from samples by means of solid-phase extraction (SPE) and identified and quantified by (1)H NMR without further derivatization steps. The lower limit of quantification (LLOQ) was 5 mu g/mL Good inter and intra-assay precision was also observed (relative standard deviation <8.5%) with the use of 4-nitro-DL-phenylalanine as an internal standard (IS). This method of 1H NMR analysis is not time consuming and can be readily utilized to monitor L-BMAA and confirm its presence in environmental and biological samples. (C) 2008 Elsevier Ltd. All rights reserved.

Gas Chromatographic Analysis of Dimethyltryptamine and beta-Carboline Alkaloids in Ayahuasca, an Amazonian Psychoactive Plant Beverage

Introduction - Ayahuasca is obtained by infusing the pounded stems of Banisteriopsis caapi in combination with the leaves of Psychotria viridis. P. viridis is rich in the psychedelic indole N,N-dimethyltryptamine, whereas B. caapi contains substantial amounts of beta-carboline alkaloids, mainly harmine, harmaline and tetrahydroharmine, which are monoamine-oxidase inhibitors. Because of differences in composition in ayahuasca preparations, a method to measure their main active constituents is needed. Objective - To develop a gas chromatographic method for the simultaneous determination of dimethyltryptamine and the main beta-carbolines found in ayahuasca preparations. Methodology - The alkaloids were extracted by means of solid phase extraction (C(18)) and detected by gas chromatography with nitrogen/phosphorous detector. Results - The lower limit of quantification (LLOQ) was 0.02 mg/mL for all analytes. The calibration curves were linear over a concentration range of 0.02-4.0 mg/mL (r(2) > 0.99). The method was also precise (RSD < 10%). Conclusion - A simple gas chromatographic method to determine the main alkaloids found in ayahuasca was developed and validated. The method can be useful to estimate administered doses in animals and humans for further pharmacological and toxicological investigations of ayahuasca. Copyright (C) 2009 John Wiley & Sons, Ltd.

THE ROLE OF COLLOIDAL SILICON DIOXIDE IN THE ENHANCEMENT OF THE DRYING OF HERBAL PREPARATIONS IN SUSPENDED STATE

Recently, some research groups have been developing studies aiming to apply spouted beds of inert particles for production of dried herbal extracts. However, mainly due to their complex composition, several problems arise during the spouted bed drying of herbal extracts such as bed instability, product accumulation, particle agglomeration, and bed collapse. The addition of drying carriers, like colloidal silicon dioxide, to the extractive solution can minimize these unwanted effects. The aim of this work was to study the influence of the addition of colloidal silicon dioxide on enhancement of the performance of the drying of hydroalcoholic extract of Bauhinia forficata Link on a spouted bed of inert particles. The physical properties of the herbal extract and of its mixture with colloidal silicon dioxide at several concentrations (20% to 80% related to solids content) were quantified by determination of the surface tension, rheological properties, density, pH, and contact angles with the inert surfaces. Drying performance was evaluated through determination of the elutriation ratio, product recovery ratio, and product accumulation. The product was characterized through determination of the thermal degradation of bioactive compounds and product moisture content. The results indicated that the rheological properties of the extracts and their preparations, the contact angle with inert material, and the work of adhesion play important roles in the spouted bed drying of herbal extracts. Higher concentration of the drying carrier significantly improved the spouted bed drying performance.

In vitro studies of cutaneous retention of magnetic nanoemulsion loaded with zinc phthalocyanine for synergic use in skin cancer treatment

In this study was developed a new nano drug delivery system (NDDS) based on association of biodegradable surfactants with biocompatible magnetic fluid of maguemita citrate derivative. This formulation consists in a magnetic emulsion with nanostructured colloidal particles. Preliminary in vitro experiments showed that the formulation presents a great potential for synergic application in the topical release of photosensitizer drug (PS) and excellent target tissue properties in the photodynamic therapy (PDT) combined with hyperthermia (HPT) protocols. The physical chemistry characterization and in vitro assays were carried out by Zn(II) Phtalocyanine (ZnPc) photosensitizer incorporated into NDDS in the absence and the presence of magnetic fluid, showed good results and high biocompatibility. In vitro experiments were accomplished by tape-stripping protocols for quanti. cation of drug association with different skin tissue layers. This technique is a classical method for analyses of drug release in stratum corneum and epidermis+ dermis skin layers. The NDDS formulations were applied directly in pig skin (tissue model) fixed in the cell`s Franz device with receptor medium container with a PBS/EtOH 20% solution (10mM, pH 7.4) at 37 degrees C. After 12 h of topical administration stratum corneum was removed from fifty tapes and the ZnPc retained was evaluated by solvent extraction in dimetil-sulphoxide under ultrasonic bath. These results indicated that magnetic nanoemulsion (MNE) increase the drug release on the deeper skin layers when compared with classical formulation in the absence of magnetic particles. This could be related with the increase of biocompatibility of NDDS due to the great affinity for the polar extracelullar matrix in the skin and also for the increase in the drug partition inside of corneocites wall. (C) 2008 Elsevier B.V. All rights reserved.

Development of composite adsorbents of carbon and intercalated clay for N2 and O2 adsorption: A preliminary study

Composite adsorbents of carbon and alumina intercalated montmorillonite were prepared and characterized by adsorption of N-2 and O-2 at various temperatures. The effects of pyrolysis, temperature, heating rate, subsequent degassing, and doping of cations and anions were investigated. The adsorption capacities of the composite adsorbents developed at higher temperatures (0 and -79 degrees C) are found to be larger than those of normal alumina pillared clays. The experimental results showed that the framework of these adsorbents is made of alumina particles and clay sheets while the pyrolyzed carbon distributes in the space of interlayers and interpillars. The pores between the carbon particles, clay sheets, and alumina pillars are very narrow with very strong adsorption forces, leading to enhanced adsorption capacities at 0 and -79 degrees C. The composite adsorbents exhibit features similar to those of carbonaceous adsorbents. Their pore structures, adsorption capacities, and selectivities to oxygen can be tailored by a controlled degassing procedure. Meanwhile, ions can be doped into the adsorbents to modify their adsorption properties, as usually observed for oxide adsorbents like zeolite and pillared clays. Such flexibility in pore structure tailoring is a potential advantage of the composite adsorbents developed for their adsorption and separation applications. (C) 1999 Academic Press.

Detection of lead(II) and silver(I) in aqueous solution using a piezoelectric device

The gold surface of a quartz crystal microbalance was modified by the attachment of silica particles derivatised with N-[(3-trimethoxysilyl)propyl] ethylenediaminetriacetic acid. The device was employed to study the kinetics of the interaction of aqueous solutions of lead(II) nitrate and silver(I) nitrate with the surface and for the selective separation of the metal ions.

Comparative analysis of dendritic cell density and total number in commonly transplanted organs: morphometric estimation in normal mice

Dendritic cells (DC) are considered to be the major cell type responsible for induction of primary immune responses. While they have been shown to play a critical role in eliciting allosensitization via the direct pathway, there is evidence that maturational and/or activational heterogeneity between DC in different donor organs may be crucial to allograft outcome. Despite such an important perceived role for DC, no accurate estimates of their number in commonly transplanted organs have been reported. Therefore, leukocytes and DC were visualized and enumerated in cryostat sections of normal mouse (C57BL/10, B10.BR, C3H) liver, heart, kidney and pancreas by immunohistochemistry (CD45 and MHC class II staining, respectively). Total immunopositive cell number and MHC class II+ cell density (C57BL/10 mice only) were estimated using established morphometric techniques - the fractionator and disector principles, respectively. Liver contained considerably more leukocytes (similar to 5-20 x 10(6)) and DC (similar to 1-3 x 10(6)) than the other organs examined (pancreas: similar to 0.6 x 10(6) and similar to 0.35 x 10(6): heart: similar to 0.8 x 10(6) and similar to 0.4 x 10(6); kidney similar to 1.2 x 10(6) and 0.65 x 10(6), respectively). In liver, DC comprised a lower proportion of all leukocytes (similar to 15-25%) than in the other parenchymal organs examined (similar to 40-60%). Comparatively, DC density in C57BL/10 mice was heart > kidney > pancreas much greater than liver (similar to 6.6 x 10(6), 5 x 10(6), 4.5 x 10(6) and 1.1 x 10(6) cells/cm(3), respectively). When compared to previously published data on allograft survival, the results indicate that the absolute number of MHC class II+ DC present in a donor organ is a poor predictor of graft outcome. Survival of solid organ allografts is more closely related to the density of the donor DC network within the graft. (C) 2000 Elsevier Science B.V. All rights reserved.

Modeling of heat transfer in fluidized-bed coating of cylinders

A numerical model of heat transfer in fluidized-bed coating of solid cylinders is presented. By defining suitable dimensionless parameters, the governing equations and its associated initial and boundary conditions are discretized using the method of orthogonal collocation and the resulting ordinary differential equations simultaneously solved for the dimensionless coating thickness and wall temperatures. Parametric Studies showed that the dimensionless coating thickness and wall temperature depend on the relative heat capacities of the polymer powder and object, the latent heat of fusion and the size of the cylinder. Model predictions for the coating thickness and wall temperature compare reasonably well with numerical predictions and experimental coating data in the literature and with our own coating experiments using copper cylinders immersed in nylon-11 and polyethylene powders. (C) 2001 Elsevier Science Ltd. All rights reserved.

Conductivity, NMR and crystallographic study of N,N,N,N-tetramethylammonium dicyanamide plastic crystal phases: an archetypal ambient temperature plastic electrolyte material

N,N,N,N-Tetramethylammonium dicyanamide (Me(4)NDCA) has been examined via differential scanning calorimetry (DSC), thermogravimetric analysis, conductivity, single crystal X-ray diffraction and H-1 nuclear magnetic resonance (NMR) analyses, and was found to be highly conductive in the solid state (sigma = 10(-3) S cm(-2) at 420 K) and to also exhibit unusual plastic crystal behaviour. To investigate the correlation between such behaviour and the occurrence of molecular rotations in the crystal, H-1 NMR second moment measurements are compared with calculated values predicted from the crystal structure. While DSC analysis indicates a number of solid-solid transitions at ambient temperatures, subsequent H-1 NMR analysis of the Me4N+ cation shows that a variety of rotational motions become active at low (

Synthesis, characterization and electrochemical behavior of the vanadium pentoxide/cetyl pyridinium chloride hybrid material

In situ and ex situ studies concerning the new hybrid material vanadium pentoxide xerogel in the presence of the cationic surfactant cetyl pyridinium chloride (V(2)O(5)/CPC) are presented. The in situ characterization studies revealed the presence of a lamellar structure for the V(2)O(5)/CPC hybrid material. The intercalation reaction was evidenced on the basis of the increase in the d-spacing as well as the displacement of the infrared bands toward lower energy levels. Electrochemical studies comprising the cyclic voltammetry and the electrochemical impedance spectroscopy techniques showed that the behavior of the hybrid material is considerably influenced by the electrolyte composition. The ion insertion/de-insertion into the V(2)O(5) xerogel structure accompanying the charge transfer process is influenced by the solid-state diffusion process modeled by using the finite-space Warburg element.

Effects of Si content on defect band formation in hypoeutectic Al-Si die castings

Al-3-11% Si alloys have been high-pressure die-cast and characterized microstructurally. Alstruc was used to calculate the solidification characteristics and fraction of eutectic. Defect bands were observed at all Si contents, although their constitution, position and distinctiveness were a function of Si content. The defect bands contain a higher fraction Al-Si eutectic than the surroundings in all alloys, and porosity was additionally found in the band in AlSi3. With decreasing Si content, the defect bands formed closer to the casting surface, became more prevalent and also the width of the bands decreased. These differences are discussed by considering the effect of Si content on the distribution of solid in the mushy wall layers and on the feeding potentials of the alloys. The observations are consistent with the mechanism proposed by Gourlay et al. in which bands form due to deformation within the solidifying mushy wall layers. (c) 2005 Elsevier B.V. All rights reserved.

Determination of the force constant of a single-beam gradient trap by measurement of backscattered light

A single-beam gradient trap could potentially be used to hold a stylus for scanning force microscopy. With a view to development of this technique, we modeled the optical trap as a harmonic oscillator and therefore characterized it by its force constant. We measured force constants and resonant frequencies for 1-4-mu m-diameter polystyrene spheres in a single-beam gradient trap using measurements of back-scattered light. Force constants were determined with both Gaussian and doughnut laser modes, with powers of 3 and 1 mW, respectively. Typical values for spring constants were measured to be between 10(-6) and 4 x 10(-6) N/m. The resonant frequencies of trapped particles were measured to be between 1 and 10 kHz, and the rms amplitudes of oscillations were estimated to be around 40 nm. Our results confirm that the use of the doughnut mode for single-beam trapping is more efficient in the axial direction. (C) 1996 Optical Society of America.